Thien-2-one compounds with an alkylidene or imino group in the 5-position of the ring

ABSTRACT

The invention relates to novel thienone compounds useful in dyeing fibers, of the formula: ##STR1## where R 1  is cyano, C 1  -C 4  -alkoxycarbonyl, carbamoyl or C 1  -C 4  -monoalkylcarbamoyl or -dialkylcarbamoyl, 
     R 2  is hydrogen, C 1  -C 8  -alkyl, substituted or unsubstituted phenyl, furyl, thienyl or halogen, 
     X is nitrogen or CR 4  where R 4  is hydrogen, C 1  -C 4  -alkyl, C 1  -C 4  -alkoxycarbonyl, cyano or substituted or unsubstituted phenyl, and 
     R 3  is an aniline, thiazole, indole, styrol or isoindole radical, with the proviso that if R 1  is cyano, X is CH and R 3  is 4-dimethylaminophenyl or styryl, then R 2  is not methyl or phenyl and that if R 1  is cyano, X is CH and R 3  is phenyl or 4-methoxyphenyl, then R 2  is not phenyl.

The present invention provides novel thien-2-one compounds which have an alkylidene or imino group in the 5 position on the ring and a method of using same for dyeing fibers.

German Pat. No. 2,732,221 discloses dyes based on 1,3-thiazole derivatives which have an alkylidene group in the 2 position on the ring and an alkylidene or imino group in the 5 position on the ring.

We have now found a thienone compound of the formula I ##STR2## where

R¹ is cyano, C₁ -C₄ -alkoxycarbonyl, carbamoyl or C₁ -C₄ -monoalkylcarbamoyl or -dialkylcarbamoyl,

R² is hydrogen, C₁ -C₈ -alkyl, substituted or unsubstituted phenyl, furyl, thienyl or halogen,

X is nitrogen or CR⁴ where R⁴ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl, cyano or substituted or unsubstituted phenyl, and

R³ is a radical of the formula ##STR3## where the ring A may be benzofused,

Y is NR⁵ R⁶ or OR⁸ where R⁵ and R⁶ are identical or different and each is independently of the other hydrogen, C₁ -C₈ -alkyl which is unsubstituted or substituted by hydroxyl, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyloxy or phenyl, allyl, C₅ -C₇ -cycloalkyl or phenyl or together with the nitrogen atom joining them are a 5- or 6-membered saturated heterocyclic ring and R⁸ is C₁ -C₄ -alkyl or phenyl,

the R⁷ s are independently of one another hydrogen, chlorine, bromine, hydroxyl, C₁ -C₄ -alkyl, C_(1-C) ₄ -alkoxy, unsubstituted or chlorine-, C₁ -C₄ -alkoxy- or phenoxy-substituted C₁ -C₄ -alkanoylamino, benzoylamino, C₁ -C₄ -mono- or -dialkylaminosulfonylamino, C₁ -C₄ -alkanoyloxy or phenylsulfonyloxy,

R⁹ is hydrogen, C₁ -C₄ -dialkylamino or C₁ -C₄ -alkoxy,

R¹⁰ is hydrogen or cyano,

R¹¹ is hydrogen, chlorine, bromine or C₁ -C₄ -alkyl,

R¹² is hydrogen, chlorine, bromine, C₁ -C₈ -alkyl, substituted or unsubstituted phenyl or thienyl,

W is NR⁵ R⁶ or ##STR4## where R⁵, R⁶, R⁷, Y and the ring A are each as defined above,

Z is nitrogen or CR¹ where R¹ is as defined above, and

n is 1, 2, 3 or 4,

with the proviso that if R¹ is cyano, X is CH and R³ is 4-dimethylaminophenyl or styryl, then R² is not methyl or phenyl and that if R¹ is cyano, X is CH and R³ is phenyl or 4-methoxyphenyl, then R² is not phenyl.

3-Cyanothien-2-ones which are substituted by phenyl in ring position 4 and by benzylidene, 4-methoxybenzylidene, 4-dimethylaminobenzylidene or 3-phenylprop-2-enylidene in ring position 5 or by methyl in ring position 4 and by 4-dimethylaminobenzylidene or 3-phenylprop-2-enylidene in ring position 5 are known and described in J. Prakt. Chem. 317 (1975), 867 and also in the dissertation by M. Hentschel, Technical University of Dresden, Jan. 28, 1975.

All the alkyl groups appearing in the abovementioned radicals of the formula I can be not only straight-chain but also branched. Where the phenyl radicals appearing in the formula I are substituted, suitable substitutents for each instance are for example C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine and nitro.

In the formula I, R¹ and R⁴ are each for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or sec-butoxycarbonyl.

R¹ is further for example methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, diisopropylcarbamoyl, dibutylcarbamoyl or N-methyl-N-ethylcarbamoyl.

R², R⁵, R⁶, R⁷, R⁸, R¹¹ and R¹² are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

R², R⁵, R⁶ and R¹² are each further for example pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl or 2-ethylhexyl.

R² is further for example fluorine, chlorine or bromine.

R⁵ and R⁶ are each further for example 2-hydroxyethyl, 2-chloroethyl, 2-cyanoethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-formyloxyethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyl-oxyethyl, 2-methoxypropyl, 3-methoxypropyl, benzyl, 1- or 2-phenylethyl, phenyl, cyclopentyl, cyclohexyl or cycloheptyl.

R⁵ and R⁶ are further with the nitrogen atom joining them for example pyrrolidino, piperidino, morpholino, piperazino or N-(C₁ -C₄ -alkyl)piperazino, such as N-methylpiperazino or N-ethylpiperazino.

R⁷ and R⁹ are each further for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

R⁷ is further for example formylamino, acetylamino, propionylamino, butyrylamino, isobutyrylamino, chloroacetylamino, methoxyacetylamino, ethoxyacetylamino, phenoxyacetylamino, 3-chloropropionylamino, 3- or 4-methoxybutyrylamino, methyl- or ethylaminosulfonylamino, dimethylaminosulfonylamino, diethylaminosulfonylamino, formyloxy, acetyloxy, propionyloxy, butyryloxy or isobutyryloxy.

R⁹ is further for example methylamino, ethylamino, propylamino, isopropylamino, butylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino or N-methyl-N-ethylamino.

R², R⁴ and R¹² are each further for example 2- or 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 2,4-dimethylphenyl, 2- or 4-methoxyphenyl, 4-ethoxyphenyl, 2,4-dimethoxyphenyl, 2- or 4-chlorophenyl, 2- or 4-bromophenyl, 2,6-dichlorophenyl or 3-nitrophenyl.

R³ is inter alia for example of the formula ##STR5## where R¹, R⁵, R⁶, R⁷, R⁸, R¹² and n are each as defined above.

Preference is given to those thienone compounds of the formula I where

R¹ is cyano or carbamoyl,

R² is C₁ -C₄ -alkyl, unsubstituted or methyl-, ethyl-, methoxy-, ethoxy-, chlorine- or bromine-substituted phenyl or thienyl, X is nitrogen or CR⁴ where R⁴ is hydrogen or cyano and

R³ is a radical of the formula ##STR6## where Y, R⁷ and the ring A are each as defined above.

Preference is given in particular to thienone compounds of the formula I where R¹ is cyano, R² is methyl, unsubstituted or methoxy-substituted phenyl or thienyl, X is nitrogen or CR⁴ where R⁴ is hydrogen or cyano and, R³ is a radical of the formula ##STR7## where the ring A is not benzofused and Y and R⁷ are each as defined above.

To prepare a compound of the formula I, for example a 2-hydroxythiophene of the formula II ##STR8## where R¹ and R² are each as defined above, is condensed with a compound of the formula III

    R.sup.3 -X=0                                               (III)

where R³ and X have the abovementioned meanings [except X=C(CN)]. If a compound of the formula III is an aldehyde or ketone, it can be advantageous in some cases to use it in acetal form.

The condensation is advantageously carried out in an inert solvent at from 20° to 160° C., preferably at from 20° to 100° C. Suitable solvents are for example methanol, ethanol, propanol, isopropanol, butanol, isobutanol, methylglycol, dioxane, acetone, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, chlorobenzene and nitrobenzene. Preference is given to working in alcohols, for example in propanol.

The condensation can also be carried out in the presence of acid or basic catalysts. The water formed in the course of the reaction can, if a suitable solvent is used, for example toluene, be removed from the reaction mixture azeotropically. However, it is also possible to carry out the reaction in the presence of water.

Suitable acid catalysts are for example mineral acids, such as hydrochloric acid or sulfuric acid, carboxylic acids, such as formic acid, acetic acid or trichloroacetic acid, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride and thionyl chloride.

Suitable basic catalysts are for example ammonium acetate and amines, such as piperidine, pyrrolidine, pyridine, triethylamine and triethanolamine.

To prepare those compounds of the formula I where X is C(CN), it is possible to react those compounds of the formula I where X is CH with metal cyanides, such as sodium cyanide or potassium cyanide, and in a subsequent reaction to reoxidize with suitable oxidizing agents, for example bromine, K₃ [Fe(CN)₆ ], Pb(OAc)₄ or FeCl₃ ×6H₂ O. This method of cyanation is described in Dyes and Pigments 1 (1980), 3 for coumarin derivatives.

Some compounds of the formula II are known from the abovementioned references. In addition, DD-A-113,233 describes a process for preparing 2-hydroxy-3-cyanothiophenes whose ring position 5 is unsubstituted (for example 2-hydroxy-3-cyano-4-phenylthiophene).

Further details of the preparation can be found in the Examples.

We have further found that the thienone compounds of the formula Ia ##STR9## where

R¹ is cyano, C₁ -C₄ -alkoxycarbonyl, carbamoyl or C₁ -C₄ -mono- or -dialkylcarbamoyl,

R² is hydrogen, C₁ -C₈ -alkyl, substituted or unsubstituted phenyl, furyl, thienyl or halogen,

X is nitrogen or CR⁴ where R⁴ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl, cyano or substituted or unsubstituted phenyl, and

R³ is a radical of the formula ##STR10## where the ring A may be benzofused,

Y is NR⁵ R⁶ or OR⁸ where R⁵ and R⁶ are identical or different and each is independently of the other hydrogen, C₁ -C₈ -alkyl which is unsubstituted or substituted by hydroxyl, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyloxy or phenyl, allyl, C₅ -C₇ -cycloalkyl or phenyl or together with the nitrogen atom joining them are a 5- or 6-membered saturated heterocyclic ring and R⁸ is C₁ -C₄ -alkyl or phenyl,

the R⁷ s are independently of one another hydrogen, chlorine, bromine, hydroxyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, unsubstituted or chlorine-, C₁ -C₄ -alkoxy-, or phenoxy-substituted C₁ -C₄ -alkanoylamino benzoylamino, C₁ -C₄ -mono- or dialkylaminosulfonylamino, C₁ -C₄ -alkanoyloxy or phenylsulfonyloxy,

R⁹ is hydrogen, C₁ -C₄ -dialkylamino or C₁ -C₄ -alkoxy,

R¹⁰ is hydrogen or cyano,

R¹¹ is hydrogen, chlorine, bromine or C₁ -C₄ -alkyl,

R¹² is hydrogen, chlorine, bromine, C₁ -C₈ -alkyl, substituted or unsubstituted phenyl or thienyl,

W is NR⁵ R⁶ or ##STR11## where R⁵, R⁶, R⁷, Y and the ring A are each as defined above,

Z is nitrogen or CR¹ where R¹ is as defined above, and

n is 1, 2, 3 or 4,

are suitable for use as dyes. They are suitable in particular for dyeing fibers, such as polyesters, polyamides, cellulose esters or blend fabrics of polyesters and cellulose fibers.

Brilliant dyeings are obtained in yellow to greenish blue shades having good fastness properties, in particular on polyesters. In addition, the dyes show high tinctorial strength.

The Examples which follow serve to illustrate the invention in more detail.

(A) Preparation of 2-hydroxythiophenes unsubstituted in ring position 5 ##STR12##

A solution of 3.9 g of sodium in 100 ml of ethanol was added dropwise in the course of 1 hour to 18.5 g of 2-amino-3-ethoxycarbonyl-4-methylthiophene in 200 ml of toluene at from 80° to 85° C. under nitrogen. 200 ml of an ethanol/toluene mixture were then distilled out of the reaction mixture at from 85° to 100° C. The precipitate which remained was filtered off at room temperature with suction, washed with a little toluene and dissolved in 250 ml of water. The solution was brought to a pH of 1 with concentrated hydrochloric acid, 100 ml of methylene chloride were added, and the organic phase was separated off and concentrated.

Yield: 11.0 g of initially oil, later crystalline 2-hydroxy-3-cyano-4-methylthiophene (79% of theory).

Melting point: 52°-53° C. (petroleum ether).

Table 1 gives 3-cyano-2-hydroxythiophenes of the formula ##STR13## obtained in a similar manner.

                  TABLE 1                                                          ______________________________________                                         Example          R.sup.2                                                       ______________________________________                                                           ##STR14##                                                    3                                                                                                ##STR15##                                                    4                                                                                                ##STR16##                                                    5                                                                                                ##STR17##                                                    6                                                                                                ##STR18##                                                    ______________________________________                                    

EXAMPLE 7 ##STR19##

2.01 g of 3-cyano-2-hydroxy-4-phenylthiophene were added at 90° C. with stirring to 50 g of polyphosphoric acid. The reaction mixture was stirred at that temperature for 4 hours. After cooling down, 50 g of ice were added, the mixture was stirred for one hour, and the precipitate was filtered off with suction and thoroughly washed with water to give 1.6 g (73% of theory) of 3-carbamoyl-2-hydroxy-4-phenylthiophene having a melting point of 108°-110° C.

Table 2 gives 3-carbamoyl-2-hydroxythiophenes of the formula ##STR20## obtained in a similar manner.

                  TABLE 2                                                          ______________________________________                                         Example          R.sup.2                                                       ______________________________________                                                           ##STR21##                                                    9                                                                                                ##STR22##                                                    10               CH.sub.3                                                      ______________________________________                                    

(B) Preparation of thienones according to the invention EXAMPLE 11

2.01 g of 3-cyano-2-hydroxy-4-phenylthiophene and 3.20 g of 3-methoxy-4-nitroso-N,N-dihexylaniline were stirred at 25° C. in 60 ml of n-propanol for 12 hours. This was followed by discharging onto 500 ml of water, stirring for 15 minutes, filtering off with suction and drying to give 4.9 g of a dye (97% of theory) which dyes polyester fibers in a brilliant neutral blue shade.

λ_(max) (CH₂ Cl₂): 602 nm.

EXAMPLE 12

2.01 g of 3-cyano-2-hydroxy-4-phenylthiophene and 2.31 g of 4-nitroso-N-butyl-N-(2-cyanoethyl)aniline were stirred at 25° C. in 50 ml of n-propanol for 10 hours. After 100 ml of water had been added, the dye was filtered off with suction, washed with water and dried.

Yield: 4.00 g (97% of theory), melting point 164°-166° C. (propanol),

λ_(max) (CH₂ Cl₂): 556 nm. The dye dyes polyester in violet shades.

EXAMPLE 13

1.74 g of 3-cyano-2-hydroxy-4-methylthiophene and 1.39 g of 4-N,N-diethylaminobenzaldehyde were stirred at 20° C. in 40 ml of n-propanol for 14 hours. The precipitate was filtered off with suction and washed with a little propanol. 2.85 g were obtained of a dye (96% of theory) which dyes polyester fiber material in brilliant yellowish red shades.

Melting point: 205°-207° C. (propanol),

λ_(max) (CH₂ Cl₂): 521 nm.

Table 3 gives dyes obtained in a similar manner in terms of the respective two starting components.

                                      TABLE 3                                      __________________________________________________________________________      Example                                                                             R.sup.3XO                                                                                             ##STR23##            polyesterHue                                                                          (CH.sub.2                                                                     Cl.sub.2)λm                                                             ax                     __________________________________________________________________________                                                             [nm]                   14                                                                                   ##STR24##                                                                                             ##STR25##           yellow 430                    15                                                                                   ##STR26##                                                                                             ##STR27##           yellow 445                    16                                                                                   ##STR28##                                                                                             ##STR29##           blue   612                    17                                                                                   ##STR30##                                                                                             ##STR31##           blue                          18                                                                                   ##STR32##                                                                                             ##STR33##           blue   589                    19                                                                                   ##STR34##                                                                                             ##STR35##           blue   597                    20                                                                                   ##STR36##                                                                                             ##STR37##           red                           21                                                                                   ##STR38##                                                                                             ##STR39##           red                           22                                                                                   ##STR40##                                                                                             ##STR41##           reddish                                                                               552let                 23                                                                                   ##STR42##                                                                                             ##STR43##           violet 572                    24                                                                                   ##STR44##                                                                                             ##STR45##           blue   578                    25                                                                                   ##STR46##                                                                                             ##STR47##           reddish blue                  26                                                                                   ##STR48##                                                                                             ##STR49##           reddish blue                  27                                                                                   ##STR50##                                                                                             ##STR51##           red                           28                                                                                   ##STR52##                                                                                             ##STR53##           scarlet                       29                                                                                   ##STR54##                                                                                             ##STR55##           red                           30                                                                                   ##STR56##                                                                                             ##STR57##           red                           31                                                                                   ##STR58##                                                                                             ##STR59##           reddish blue                  32                                                                                   ##STR60##                                                                                             ##STR61##           blue                          33                                                                                   ##STR62##                                                                                             ##STR63##           blue                          34                                                                                   ##STR64##                                                                                             ##STR65##           blue   576                    35                                                                                   ##STR66##                                                                                             ##STR67##           greenish blue                 36                                                                                   ##STR68##                                                                                             ##STR69##           blue                          37                                                                                   ##STR70##                                                                                             ##STR71##           blue                          38                                                                                   ##STR72##                                                                                             ##STR73##           blue                          39                                                                                   ##STR74##                                                                                             ##STR75##           red                           40                                                                                   ##STR76##                                                                                             ##STR77##           yellow                        41                                                                                   ##STR78##                                                                                             ##STR79##           greenish blue                 42                                                                                   ##STR80##                                                                                             ##STR81##           greenish blue                 43                                                                                   ##STR82##                                                                                             ##STR83##           blue                          44                                                                                   ##STR84##                                                                                             ##STR85##           red                           45                                                                                   ##STR86##                                                                                             ##STR87##           blue                          46                                                                                   ##STR88##                                                                                             ##STR89##           yellow                        47                                                                                   ##STR90##                                                                                             ##STR91##           red                           48                                                                                   ##STR92##                                                                                             ##STR93##           red                           49                                                                                   ##STR94##                                                                                             ##STR95##           red                           50                                                                                   ##STR96##                                                                                             ##STR97##           red                           51                                                                                   ##STR98##                                                                                             ##STR99##           blue                          52                                                                                   ##STR100##                                                                                            ##STR101##          yellow 431                    53                                                                                   ##STR102##                                                                                            ##STR103##          yellow 431                    54                                                                                   ##STR104##                                                                                            ##STR105##          blue   577                    __________________________________________________________________________

EXAMPLE 55

1.66 g of the dye of Example 29 in 50 ml of N,N-dimethylformamide were admixed with 0.5 g of KCN and the mixture was stirred at room temperature for 1 hour. After the addition of 1.35 g of FeCl₃ ×6H₂ O, stirring was continued for a further 8 hours. The reaction mixture was poured onto 150 ml of ice-water, and the precipitate was filtered off and washed with water. 1.7 g (95% of theory) were obtained of the dye of the formula ##STR106## which dyes polyester in blue shades (λ_(max) (CH₂ Cl₂): 599).

Table 4 gives dyes of the formula ##STR107## obtained in a similar manner.

                                      TABLE 4                                      __________________________________________________________________________                                        Hue on                                      Example                                                                             R.sup.3        R.sup.2     R.sup.1                                                                           polyester                                   __________________________________________________________________________     56                                                                                   ##STR108##    C.sub.6 H.sub.5                                                                            CN blue                                        57                                                                                   ##STR109##    C.sub.6 H.sub.5                                                                            CN blue                                        58                                                                                   ##STR110##    C.sub.6 H.sub.5                                                                            CN blue                                        59                                                                                   ##STR111##                                                                                    ##STR112## CN blue                                        60                                                                                   ##STR113##                                                                                    ##STR114## CN blue                                        61                                                                                   ##STR115##                                                                                    ##STR116## CN blue                                        62                                                                                   ##STR117##                                                                                    ##STR118## CN blue                                        __________________________________________________________________________ 

We claim:
 1. A thienone compound of the formula ##STR119## where R¹ is cyano, C₁ -C₄ -alkoxycarbonyl, carbamoyl or C₁ -C₄ -monoalkylcarbamoyl or -dialkylcarbamoyl,R² is hydrogen, C₁ -C₈ -alkyl, unsubstituted phenyl or phenyl substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or nitro, furyl, thienyl or halogen, X is nitrogen or CR⁴ where R⁴ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl, cyano or unsubstituted phenyl or phenyl substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or nitro, and R³ is a radical of the formula ##STR120## where the ring A is phenyl or naphthyl, Y is NR⁵ R⁶ or OR⁸ where R⁵ and R⁶ are identical or different and each is independently of the other hydrogen, C₁ -C₈ -alkyl which is unsubstituted or substituted by hydroxyl, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyloxy or phenyl, allyl, C₅ -C₇ -cycloalkyl or phenyl or together with the nitrogen atom joining them are a 5- or 6-membered saturated heterocyclic ring selected from the group consisting of pyrrolidino, piperidino, morpholino, piperazino and N-(C₁ -C₄ -alkyl) piperazino and R⁸ is C₁ -C₄ -alkyl or phenyl, the R⁷ s are independently of one another hydrogen, chlorine, bromine, hydroxyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, unsubstituted or chlorine-, C₁ -C₄ -alkoxy- or phenoxy-substituted C₁ -C₄ -alkanoylamino, benzoylamino, C₁ -C₄ -mono- or -dialkylaminosulfonylamino, C₁ -C₄ -alkanoyloxy or phenylsulfonyloxy, R⁹ is hydrogen, C₁ -C₄ -dialkylamino or C₁ -C₄ -alkoxy, R¹⁰ is hydrogen or cyano, R¹¹ is hydrogen, chlorine, bromine or C₁ -C₄ -alkyl, R¹² is hydrogen, chlorine, bromine, C₁ -C₈ -alkyl, unsubstituted phenyl or phenyl substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or nitro, or thienyl, W is NR⁵ R⁶ or ##STR121## where R⁵, R⁶, R⁷, Y and the ring A are each as defined above, Z is nitrogen or CR¹ where R¹ is as defined above and n is 1, 2, 3 or 4 with the proviso that if R¹ is cyano, X is CH and R³ is 4-dimethylaminophenyl or styryl, then R² is not methyl or phenyl and that if R¹ is cyano, X is CH and R³ is phenyl or 4-methoxyphenyl, then R² is not phenyl.
 2. A thienone compound as claimed in claim 1, wherein R¹ is cyano or carbamoyl, R² is C₁ -C₄ -alkyl, unsubstituted or methyl-, ethyl-, methoxy-, ethoxy-, chlorine- or bromine-substituted phenyl or thienyl, X is nitrogen or CR⁴ where R⁴ is hydrogen or cyano, and R³ is a radical of the formula ##STR122##
 3. A thienone compound as claimed in claim 1, wherein R¹ is cyano, R² is methyl, unsubstituted or methoxy-substituted phenyl or thienyl, X is nitrogen or CR⁴ where R⁴ is hydrogen or cyano, and R³ is a radical of the formula ##STR123## where the ring A is phenyl.
 4. A method of dyeing fibers comprising applying a thienone compound of the formula ##STR124## where R¹ is cyano, C₁ -C₄ -alkoxycarbonyl, carbamoyl or C₁ -C₄ -monoalkylcarbamoyl or -dialkylcarbamoyl,R² is hydrogen, C₁ -C₈ -alkyl, unsubstituted phenyl or phenyl substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or nitro, furyl, thienyl or halogen, X is nitrogen or CR⁴ where R⁴ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl, cyano or unsubstituted phenyl or phenyl substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or nitro, and R³ is a radical of the formula ##STR125## where the ring A is phenyl or naphthyl, Y is NR⁵ R⁶ or OR⁸ where R⁵ and R⁶ are identical or different and each is independently of the other hydrogen, C₁ -C₈ -alkyl which is unsubstituted or substituted by hydroxyl, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyloxy or phenyl, allyl, C₅ -C₇ -cycloalkyl or phenyl or together with the nitrogen atom joining them are a 5- or 6-membered saturated heterocyclic ring selected from the group consisting of pyrrolidino, piperidino, morpholino, piperazino and N-(C₁ -C₄ -alkyl) piperazino and R⁸ is C₁ -C₄ -alkyl or phenyl, the R⁷ s are independently of one another hydrogen, chlorine, bromine, hydroxyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, unsubstituted or chlorine-, C₁ -C₄ -alkoxy- or phenoxy-substituted C₁ -C₄ -alkanoyl-amino, benzoylamino, C₁ -C₄ -mono- or -dialkylaminosulfonylamino, C₁ -C₄ -alkanoyloxy or phenylsulfonyloxy, R⁹ is hydrogen, C₁ -C₄ -dialkylamino or C₁ -C₄ -alkoxy, R¹⁰ is hydrogen or cyano, R¹¹ is hydrogen, chlorine, bromine or C₁ -C₄ -alkyl, R¹² is hydrogen, chlorine, bromine, C₁ -C₈ -alkyl, unsubstituted phenyl or phenyl substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or nitro, or thienyl, W is NR⁵ R⁶ or ##STR126## where R⁵, R⁶, R⁷, Y and the ring A are each as defined above, Z is nitrogen or CR¹ where R¹ is as defined above, and n is 1, 2, 3 or
 4. 